Additives for clothes dryers

ABSTRACT

A novel method for applying adjuvants to fabric employing a tumbler-type dryer is disclosed. To achieve uniform distribution of the adjuvant on the fabric, the adjuvant, in accordance with the present invention, is sprayed on to the dryer drum. Spreading agents, distributing agents or carrier may be included in the composition sprayed on to the dryer drum if desired. Novel compositions of matter suitable for use in the practice of this invention are also disclosed.

United States Patent Rudy et al.

[451 Mar. 21, 1972 [54] ADDITIVES FOR CLOTHES DRYERS [72] Inventors:Jerome Rudy, Livingston, N.J.; Anthony A. Rapisarda, Elmhurst, N.Y.

[73] Assignee: Lever Brothers Company, New York,

[22] Filed: July 17, 1969 21 Appl. No.: 842,719

[52] US. Cl ..ll7/l09, 8/147, 34/12, 1l7/33.5 T, l17/139.5 A, 117/1395C, 117/1395 F, 118/418, 118/506, 252/8.6, 252/106 2,784,183 3/1957Keller et a1 ....117/33.5 X 2,822,291 2/1958 Hahn ..117/120 X 3,173,8413/1965 Roth et al. ....117/33.5 X 3,401,052 9/1968 Berger et al.. 17/109X 3,442,692 5/1969 Gaiser ..1 17/120 X 3,454,494 7/1969 Clark et a1...252/8.8 3,468,697 9/1969 Hunter ..117/121 X 3,485,761 12/1969 Haxby..117/33.5 X

Primary ExaminerRalph S. Kendall Assistant Examiner-Thomas E. BokanAttorney-Brumbaugh, Garves, Donohue & Raymond [57] ABSTRACT A novelmethod for applying adjuvants to fabric employing a tumbler-type dryeris disclosed. To achieve uniform distribution of the adjuvant on thefabric, the adjuvant, in accordance with the present invention, issprayed on to the dryer drum. Spreading agents, distributing agents orcarrier may be included in the composition sprayed on to the dryer drumif desired. Novel compositions of matter suitable for use in thepractice of this invention are also disclosed.

9 Claims, No Drawings ADDITIVES FOR CLOTHES DRYERS This inventionrelates to a novel method of applying adjuvants to clothing intumbler-type drying machines.

It has been customary for many years to include various adjuvants indetergents and wash-cycle additives. Germicides, fabric softeners andoptical brighteners'areamong the most common such adjuvants used.However, other materials, such as ironing aids, antistatic agents, stainrepellents, soil release agents, wrinkle preventatives;deodorizers,fresheners (e.g., perfumes, etc.), cleaning agents, surfactants,flameproofing agents, mothproofing agents, bleaching agents, etc. arealso products which potentially can be applied to fabrics employing themethod of the present invention. A-particular advantage of the presentinvention is that it'is possible to obtain much more efficientapplication of the adjuvant to the clothing than can be obtained if theadjuvant is applied in the wash or rinse cycles.

in the wash orrinse cycles, the primary objective is to remove soil,etc. from the cloth being washed by means of detergents, water andemulsifying agents. The presence of detergents and emulsifying agentseffective to remove soil from the cloth manifestly renders difficult andless efficient the concurrent application of adjuvants such as fabricsofteners or other adjuvants to the same piece of material. Since in thedrying cycle following washing and rinsing, the conditionscharacteristic of the rinsing and washing cycles leading to inefficientapplication of fabric adjuvants are not present, there is the potentialfor the much more efficient utilization and application of suchadjuvants. I

Due to the heat and mechanical action and residual water on the fabricsin the dryer, it might be expected that fabric adjuvants could be easilyand uniformly applied in the dryer. Experience demonstrates, however,that this does not'readily occur. For example, if clothing to be treatedwith a fabric softening agent is placed into a dryer together with apure fabric softening active ingredient such as distearyl dimethylammonium chloride, the softener will be somewhat spread throughout theclothing treated, but it will be far fromuniformly spread. This mayresult in unsightly spots on cloth or lead to water repellency. Whilethe problem of nonuniformity of spreading may be alleviated in repeatedapplications of the adjuvant, more preferable results are obtained ifthe adjuvant is sprayed on to the surface of the dryer drum inaccordance with the present invention.

As discussed in our earlier-filed application Ser. No. 821,476,nonuniformity of distribution of an adjuvant in the clothes dryer may beovercome by including a distributing agent which is ordinarily at least10 percent of the complete composition, but may be effective if presentin a concentration of as little as 5 percent by weight. The compositionsdescribed in said copending application may be used in bulk form totreat clothing in a clothes dryer-i.e., in the form of flakes, chips,pellets, tablets and the like.

It has been found in accordance with the present invention that where aspray or a 'mist of the adjuvant in a suitable solvent is applied to thesurface of the dryer drum inclusion of a distributing agent is notnecessary to obtain a good distribution in most cases. It will beunderstood, of course, that a distributing agent may be incorporated'inthe composition applied to the dryer drum if it is desired to do so.

To be effective in the present .,invention, the adjuvant deposited afterevaporation of the solvent should be a film which adheres to the innersurface of the drum, in the absence of cloth, but releases gradually andtransfers to the clothing being dried (or otherwise treated) in thedryer within a period of time from about 5 to minutes when the dryer isrotated. Where the cloth adjuvant forms a waxy film, suitable adjuvantscan be readily characterized by their melting point ranges. Typical waxymaterials, for example, are fabric softeners, antistatic agents, andcombinations of essential oils and fragrances with a suitable waxycarrier such as the C -C fatty acids, fatty alcohols, ethoxylatedderivatives thereof, polyethylene glycols, paraffin and the like.Suitable waxy materials generally have melting and softening pointsbetween more fully described below.

In the typical application in accordance with the present in- 'vention,the adjuvant to be applied to the dryer drum is formulated in amoderately volatile solvent therefor to provide a liquid solutioncontaining the adjuvant. The liquid is applied by a suitable spray meanssuch as hand sprayer, aerosol spray, or the like, to the surface of thedryer drum. The volatile solvent evaporates leaving behind a relativelyhard residue of the fabric adjuvant which is gradually abraded by theclothing as the'dryer tumbler operates and becomes uniformly applied tothe clothing.

Classes of adjuvants which may be employed in the present invention havealready generally been referred to above. More specifically,'adjuvantsuseful in the present invention include, but are not limited to:

1. Fabric softeners such as quaternary ammonium compounds of the formulaN(R,R R R;,),,X, and the reaction product of about 2 moles of a fattyacid of the formula R,,COOH and hydroxyalkyldiamine of the formula whereR, is a C to C alkyl group, R is a C, to C, alkyl group, R is selectedfrom the grou consisting of R, and R,, R, is a C, to C,,, alkyl group, Ris a C, to C divalent hydrocarbon radical and R is a hydroxyalkyl groupof from about one to three carbon atoms, X is a anion imparting waterdispersibility to the cationic ammonium compound, and y is the valencyof X.

Typical commercial products commonly available for use in the presentinvention include distearyl dimethyl ammonium chloride and the reactionproduct of approximately 2 moles of stearic acid with approximately 1mole of hydroxyethylene diamine. The last-mentioned product is a mixedchemical structure in view of the multifunctional characteristics of thediamine reactant. Spectral analysis of a commercial product preparedthrough the fatty acid-diamine reaction indicates that it contains inthe order of 25 percent quaternary compounds of the imidazoline type,the balance thereof being mixed esters and amides. Softeners related tothis last mentioned compound also include the quaternarized products ofabout 2 moles of oleic acid reacted with 1 mole of hydroxyethylenediamine and the product of about 2 moles of a mixture of oleic andstearic acids reacted with about 1 mole of hydroxyethylene diamine.Other suitable fabric softening agents which may be used in the presentinvention include those which have been described in Proceedings of theAmerican Association of Textile Chemists and Colorists, AmericanDyestufl Reporter, pages P42 and P43, Jan. 28, 1957.

2. Optical brighteners such as disulfonated diaminostilbene compoundsdisclosed in Alien Property Custodian publication No. 381,856, and inUS. Pat. No. 2,612,501, and triazole compounds ofthe type disclosed inUS. Pat. No. 2,784,183.

3. Essential oils and fragrances. In using materials of this category,many substances are normally in liquid form. Such materials mustbecombined with a suitable carrier having the desired waxiness, thermalstability, and hardness to obtain a composition suitable for applying tothe surface of a dryer drum. Suitable waxy carriers which may be used asneeded are discussed below.

4. Antistatic agents which in many cases are compounds of the samegeneral structure discussed above with respect to fabric softeningcompounds. As disclosed in U.S. Pat. application Ser. No. 468,918, theantistatic properties of quaternary ammonium compounds as well as otherfabric softening agents may be enhanced by combining these materialswith ethanolamides such as tallow ethanolamide.

5. Germicides such as the halogenated salicylanilides, hexachlorophene,neomycin sulfate, benzalkonium quaternary compounds, and the like. Thehalogenated salicylanilides which have found the most widespreadacceptance are tribromosalicylanilide and polybromosalicylanilide, thelatter being a mixture primarily of dibromosalicylanilide andtribromosalicylanilide.

6. Bodying agents such as carboxymethyl cellulose,hydroxyethylcellulose, starch, polyvinyl acetate and the like. Polyvinylacetate is also effective to improve ease of ironing and may be employedfor that purpose.

7. Soil release agents such as the polyacrylic polyvinyl alcoholcompositions described, for example, in US. Pat. No. 3,377,249. Avariety of detergents may also be employed as soil release agents.

In the practice of the present invention, one or more of the foregoingfabric adjuvants will be combined and dissolved in a suitable volatilesolvent to form a sprayable solution. In normal practice the adjuvantwill be sprayed on to the surface ofa relatively cold dryer drum. Inorder to obtain uniform distribution, it is required that the solutionof adjuvant sprayed to the cold drum surface will dry and hardensufficiently that it will not be immediately wiped off on to theclothing which is loaded into the dryer. Accordingly, the solvent systemshould have sufficient volatility at ambient temperature that it willevaporate rapidly from the solution when applied.

Suitable solvents which may be used in the present inventionparticularly include those having sufficient volatility to be used alsoas propellants in aerosol containers of commerce. Suchsolvent-propellants are particularly efficacious since they may beemployed to formulate simple self-dispensing compositions consistingessentially of the adjuvant or adjuvants to be applied together with thesolvent-propellant. Other suitable solvents which may be employedinclude, but are not limited to: halogenated lower alkanes such asmethylene chloride and methyl chloride; lower ethers such as dimethylether; the lower alkanes such as propane, butane, pentane; loweralcohols such as methyl and ethyl alcohol; etc. It will be recognizedthat a number of the foregoing solvents are flammable and their use, ofcourse, would be inappropriate in specific commercial applications whereflammable solvents are objectionable. In this respect, solvents it maybe noted that methods for utilizing flammable solvents in aerosolcompositions have been described in the art, for example in U.S. Pat.No. 3,207,386.

When formulating aerosol compositions for use in the present inventionit will not always be found that the propellant for the aerosol will bean effective solvent for the adjuvant to be applied. This isparticularly true where the chlorinated hydrocarbons are used as thepropellant, many of which have been found to lack high-solvency power.ln cases where the solvency power of the propellant is inadequate, avolatile secondary solvent may be provided. Suitable secondary solventswould include the volatile alcohols such as methyl alcohol which areeffective to dissolve a wide variety of organic compounds.

As indicated already, in the present invention it is desired that theadjuvant applied to the surface of the dryer drum harden relativelyrapidly so that it will not be wiped off by the clothing or other clotharticles loaded into the dryer heterogeneously. Typically, therefore,the adjuvant formulation should be one from which the solvent andpropellants present will evaporate in the space of a few minutes and dryto a composition having a melting point in the order of 90 to 180 F.Where the adjuvant to be applied is one which is normally liquid, suchas, for example, an essential oil or perfume,

or a relatively soft, low-melting point adjuvant, such as, for example,l-stearylamidoethyll -methyl-2-heptadecylimidazoline methyl sulfate, theadjuvant may be formulated together with a suitable carrier whichimparts the necessary hardness to the complete composition. Suitablecarriers imparting hardness are preferably waxy organic solids such asstearic acid, stearyl alcohol, palmitic acid, palmityl alcohol, andethoxylated derivatives of the these acids and alcohols, polyethyleneglycol having a molecular weight of l,000 to 5,000, and hydrocarbonssuch as paraffin and polyethylene. Where a hardening agent is employedas a carrier, the amount thereof should be sufficient that theadjuvant-carrier mixture will exhibit a melting point of about 75 to 200F.

The present invention may be further understood by reference to thefollowing examples:

EXAMPLE 1 A solution ofl-stearylamidoethyl-l-methyl-Z-heptadecylimidazoline methyl sulfate wasdissolved in ethyl alcohol. The solution was 20 percent active. Sixtyparts of this solution was placed in a container fitted with an aerosoldischarge valve, and the container was then charged with 40 parts of afluorinated hydrocarbon propellant. The final composition inside theaerosol container after charging, therefore, contained 10 parts offabric softener, 40 parts of ethyl alcohol and 40 parts of propellant.

EXAMPLE 2 The aerosol formulation of Example 1 was sprayed on to theinterior surface of the dryer drum. The dryer was clothing charged with6 pounds of spun-dry clothing, and the clothing was dried for a periodof 45 minutes. Comparison of the clothing as dried in a dryer sprayedwith the aerosol fabric softener of Example 1 with clothing dried in theabsence of that softener showed that significantly improved softness wasobtained. In a further control, the formulation of Example 1 wasmodified by including a minor quantity of a blue colorant to determinethe uniformity of distribution. It was found that substantially uniformdistribution of the product on the dried clothing was obtained.

Further representative fabric softening compositions are the following:

Example 3 The reaction product ofmixed stearic and oleic acids withhydroxyethylethylenediamine quaternized with dimethyl sulfate 6%di(hardened tallow) dimethyl ammonium chloride 4% ethyl alcohol 40%fluorinated hydrocarbon propellant 50% This material is applied as anaerosol sprayed on to the surface ofthe dryer drum.

Example 4 l-stearylamidoethyll -methyl-2-heptadecylmanner as theformulation described in Example 2.

SOIL RELEASE FORMULATIONS Example 5 Soil release agent I054 polyethyleneglycol. m. w. 4000 40% fluorinated hydrocarbon propellant 50% Thecomposition is applied as an aerosol by spraying the interior surface ofthe dryer drum.

Example 6 the condensate of ethylene oxide with lauryl alcoholcontaining about 60% by weight ethylene oxide l0% ethyl alcohol 40%fluorinated hydrocarbon propellant 50% OPTICAL BRIGHTENER FORMULATIONSExample 7 an optical brightener of the class disclosed in APCpublication 38l,856 2% triethanol amine 48% l'luorinated hydrocarbonpropellant 50% This product is applied as an aerosol by spraying theinterior surface of the dryer drum.

Example 8 Example 7 may be modified by substituting an opticalbrightener ofthe type disclosed in US Pat. No. 2,784,183, for thebrightener of Example 7. Example 7may also be modified by substitutingdicocodimethyl ammonium chloride for all or a portion of the triethanolamine.

GERMICIDAL AND SANITIZER FORMULATIONS Example 9 polybromosalicylanilidel07 Example l2 The aerosol formulations described in Examples 9 throughI3 were sprayed on the interior surface of a dryer drum. The dryer wasthen charged with 6 pounds of spun-dried cloth and the cloth dried 45minutes. Portions of the dried cloth treated with germicide wereevaluated for antibacterial activity Treated cloth showed significantantibacterial activity while untreated cloth did not.

WATER AND STAIN REPELLANT FORMULATIONS Example 14 calcium stearate 10%ethyoxylated alcohols (C -C having about 60% ethylene oxide 2% ethylalcohol 38% fluorinated hydrocarbon propellant 50% Example 15 linearalkyl benzene sulfonate l0% isopropyl alcohol 40% fluorinatedhydrocarbon propellant 50% Example 16 polyoxyethylene sorbitantristearate 8% condensate of ethylene diamine with ethylene oxide andpropylene oxide 2% isopropyl alcohol 40% fluorinated hydrocarbonpropellant 50% BODYING AGENTS Example 17 polyvinyl alcohol 40% water 30%isobutane 30% We claim: 1. A method for treating cloth with a clothadjuvant in a clothes dryer having a drum comprising the steps of a.spraying a cloth adjuvant onto the interior surface of said dryer drum,said adjuvant forming an adherent film on said drum surface which issufficiently hard that it will not be immediately wiped off onto thecloth articles that are loaded into the drum but which is removable bythe cloth articles which abrade against said film when said drum rotatesin a period between about 5 and 45 minutes, the adjuvant being selectedfrom the group consisting of germicides, fabric softeners, opticalbrighteners, ironing aides, antistatic agents, stain repellents, soilrelease agents, wrinkle preventents, deodorizers, fresheners, cleaningagents, surfactants, flame proofing agents, moth proofing agents andbleaching agents,

b. loading the cloth to be treated in said dryer, and 17 adjuvant saidadjuvant 2. A method according to claim 1 for treating cloth with afabric softener, wherein said cloth adjuvant applied to the interiorsurface of said dryer drum is a fabric softener having a softening pointbetween 70 and 200 F.

3. A method according to claim 2 wherein said fabric softener isselected from the group consisting of quaternary ammonium compounds ofthe formula N(R,R R R ),,X and the reaction product of about 2 moles ofa fatty acid of the formula R,COOH and hydroxyalkyldiamine ofthe formuladispersibility to the cationic ammonium compound, and y is the VALENCYof X.

4. A method according to claim 1 wherein said cloth adjuvant is agermicide selected from the group consisting of halogenatedsalicylanilides, hexachlorophene, neomycin sulfate, and benzalkoniumquaternary compounds.

5. A method according to claim 1 wherein said cloth adjuvant is anoptical brightener.

6. A method according to claim 1 wherein said adjuvant is employed incombination with a waxy carrier having a softening point between about70 and 200 F., the waxy carrier being present in an amount sufficient toimpart the desired degree of hardness to the composition when saidcomposition is applied to the surface of the dryer drum.

7. A method according to claim 6 wherein said adjuvant is employed incombination with a waxy carrier selected from the group consisting ofstearic acid, stearyl alcohol, palmitic acid, palmityl alcohol, andethoxylated derivatives of these acids and alcohols, polyethylene glycolhaving a molecular weight of 1,000 to 5,000 and hydrocarbons.

8. A method according to claim 1 wherein said cloth adjuvant is employedin combination with a waxy carrier having a melting point between aboutand F.

9. A method according to claim 1 wherein said adjuvant is sprayed ontothe interior surface of said dryer drum by means of an aerosol spray.

UNITED STATES PATENT OFFlCE CETlFlCAlE or coscrim Patent NO. 3 DatedMarch 21 1972 R r lnventofls) Jerome udy et al It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

First page, Item [54] and in column 1, line 1, the title should readMethod of Applying Adjuvants to Cloth last line of Item [56] "Garves"should read Graves Column 3, line 50, after "respect" the word"solvents" should read however, line 55, after "invention" insert acomma. Column 4, line 32, after "was"; delete "clothing" and substitutethen Column 5 lines67 and 68, "mixture b-l2 alkyl dimethyl ethyl benzyl"should read mixture of alkyl dimethyl ethyl benzyl Column 7, lines 5 and64 delete "l7 ad juvant said adjuvant" and substitute therefor: c.Operating said dryer for a period of time sufficient to effectapplication of said adjuvant to said cloth. Column 8, line 2, "VALENCY"should read valency Signed and sealed this 17th day of October 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. I ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents FORM PO 050 (10-69)- USCOMM-DC 50376-P69 u.s, eovammzmPRINTING OFFICE: was o-aae-au.

2. A method according to claim 1 for treating cloth with a fabricsoftener, wherein said cloth adjuvant applied to the interior surface ofsaid dryer drum is a fabric softener having a softening point between70* and 200* F.
 3. A method according to claim 2 wherein said fabricsoftener is selected from the group consisting of quaternary ammoniumcompounds of the formula N(R1R2R3R3)yX and the reaction product of about2 moles of a fatty acid of the formula R4COOH and hydroxyalkyldiamine ofthe formula where R1 is a C16 to C20 alkyl group, R2 is a C1 to C4 alkylgroup, R3 is selected from the group consisting of R1 and R2, R4 is aC15 to C19 alkyl group, R5 is a C1 to C3 divalent hydrocarbon radicaland R6 is a hydroxyalkyl group of from about one to three carbon atoms,X is a anion imparting water dispersibility to the cationic ammoniumcompound, and y is the VALENCY of X.
 4. A method according to claim 1wherein said cloth adjuvant is a germicide selected from the groupconsisting of halogenated salicylanilides, hexachlorophene, neomycinsulfate, and benzalkonium quaternary compounds.
 5. A method according toclaim 1 wherein said cloth adjuvant is an optical brightener.
 6. Amethod according to claim 1 wherein said adjuvant is employed incombination with a waxy carrier having a softening point between about70* and 200* F., the waxy carrier being present in an amount sufficientto impart the desired degree of hardness to the composition when saidcomposition is applied to the surface of the dryer drum.
 7. A methodaccording to claim 6 wherein said adjuvant is employed in combinationwith a waxy carrier selected from the group consisting of stearic acid,stearyl alcohol, palmitic acid, palmityl alcohol, and ethoxylatedderivatives of these acids and alcohols, polyethylene glycol having amolecular weight of 1,000 to 5,000 and hydrocarbons.
 8. A methodaccording to claim 1 wherein said cloth adjuvaNt is employed incombination with a waxy carrier having a melting point between about 90*and 100* F.
 9. A method according to claim 1 wherein said adjuvant issprayed onto the interior surface of said dryer drum by means of anaerosol spray.